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Second Revision No. 11-NFPA 704-2015 [ Global Comment ]
Change all HazComm to HazCom throughout the document.
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Committee Statement
Committee Statement: HazCom is the correct acronym not HazComm
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Second Revision No. 2-NFPA 704-2015 [ Section No. 7.2 ]
7.2 Degrees of Hazard.
The degrees of hazard shall be ranked according to ease, rate, and quantity of energy release of the
material in pure or commercial form detailed in Table 7.2.
Table 7.2 Degrees of Instability Hazards
Degree of Hazard
Criteria
Materials that are sensitive to localized thermal
or mechanical shock at normal temperatures
4 — Materials that in themselves are readily capable of and pressures
detonation or explosive decomposition or explosive
Materials that have an instantaneous power
reaction at normal temperatures and pressures
density (product of heat of reaction and reaction
rate) at 250°C (482°F) of 1000 W/mL or greater
3 — Materials that in themselves are capable of
detonation or explosive decomposition or explosive
reaction but that require a strong initiating source or
must be heated under confinement before initiation
2 — Materials that readily undergo violent chemical
change at elevated temperatures and pressures
Materials that have an instantaneous power
density (product of heat of reaction and reaction
rate) at 250°C (482°F) at or above 100 W/mL
and below 1000 W/mL
Materials that are sensitive to thermal or
mechanical shock at elevated temperatures
and pressures
Materials that have an instantaneous power
density (product of heat of reaction and reaction
rate) at 250°C (482°F) at or above 10 W/mL
and below 100 W/mL
Materials that exhibit an exotherm at
temperatures less than or equal to 150°C
(302°F) when tested by differential scanning
calorimetry (DSC)
Materials that have an instantaneous power
density (product of heat of reaction and reaction
rate) at 250°C (482°F) at or above 0.01 W/mL
1 — Materials that in themselves are normally stable but and below 10 W/mL
that can become unstable at elevated temperatures and
Materials that exhibit an exotherm at
pressures
temperatures greater than 150°C (302°F) but
less than or equal to 300°C (604°F) when
tested by differential scanning calorimetry
Materials that have an instantaneous power
density (product of heat of reaction and reaction
rate) at 250°C (482°F) below 0.01 W/mL
0 — Materials that in themselves are normally stable,
even under fire conditions
Materials that exhibit an exotherm at
temperatures greater than 300°C (604°F) but
less than or equal to 500°C (932°F) when
tested by differential scanning calorimetry
Materials that do not exhibit an exotherm at
temperatures less than or equal to 500°C
(932°F) when tested by differential scanning
calorimetry
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Committee Statement
Committee
Statement:
The Committee removed the information related to Differential Scanning Calorimetry (DSC)
exotherm onset temperature criteria provided in Table 7.2. The cut points for DSC The cut points for
DSC exotherm onset temperature criteria were inconsistent with those provided in Annex E. The use
of DSC exotherm onset temperatures have been shown to be inaccurate for assessing instability
hazard ratings as indicated in the paper published in the Journal of Loss Prevention in the Process
Industries 15 (2002) 163-168 by Hofelich and LaBarge.
The deletion of DSC exotherm onset temperature criteria in Table 7.2 does not mean that DSC
cannot be used to determine instability hazard ratings but it cannot be used directly. DSC data can
be used to determine the kinetics of the reaction which in turn can be used to calculate IPD.
DSC exotherm onset temperature criteria were previously discussed only in the Annex and not in
Table 7.2. Information was moved from annex to Table 7.2, since Instantaneous Power Density (IPD)
method was not widely used at the time and there were only a limited number of chemicals that had
been rated using IPD. Today, there are many more materials that have been rated using IPD. In the
absence of quantitative data, the qualitative descriptions in the Degree of Hazard Columns can be
used to rate materials. A task group will be formed to review this issue further.
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Second Revision No. 6-NFPA 704-2015 [ Section No. A.8.2.4.1 ]
A.8.2.4.1
Even though carbon dioxide is technically not typically considered just a simple asphyxiant, the hazards
created by the release of carbon dioxide are similar to those caused by a simple asphyxiant and the
response for emergency responders should be similar to that for simple asphyxiants. Carbon dioxide
poses additional health risks beyond being an asphyxiant.
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Committee Statement
Committee
Statement:
The Committee recognizes that CO2 does not meet the definition of a simple asphyxiant in NFPA
704. However there are several sources that identify CO2 as an asphyxiant including NIOSH. The
Committee recognizes that CO2 can act as an asphyxiant at elevated levels by displacing oxygen
in confined areas.
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Second Revision No. 4-NFPA 704-2015 [ Section No. D.1 ]
D.1
A combustible dust is considered to be a finely divided solid material that is 420 micrometers (µm) or
smaller in diameter (material passing a U.S. No. 40 Standard sieve) that presents an explosion hazard
when dispersed and ignited in air.
When a dust becomes suspended in air, there is a risk of a dust cloud ignition leading to a flash fire. The
minimum explosible concentration (MEC) is the minimum concentration of combustible dust suspended in
air, measured in mass per unit volume, that will support a deflagration as defined by the text procedure in
ASTM E1515, Standard Test Method for Minimum Explosible Concentration of Combustible Dusts.
Evaluation of the hazard of a combustible dust should be determined by the means of actual test data.
Each situation should be evaluated and applicable tests selected. The following list represents the factors
that are sometimes used in determining the deflagration hazard of a dust:
(1) MEC
(2) Minimum ignition energy (MIE)
(3) Particle size distribution
(4) Moisture content as received and as tested
(5) Maximum explosion pressure at optimum concentration
(6) Maximum rate of pressure rise at optimum concentration
(7) KSt (normalized rate of pressure rise) as defined in ASTM E1226, Test Method for Pressure and
Rate of Pressure Rise for Combustible Dusts
(8) Layer ignition temperature
(9) Dust cloud ignition temperature
(10) Limiting oxidant concentration (LOC) to prevent ignition
(11) Electrical volume resistivity
(12) Charge relaxation time
(13) Chargeability
See NFPA 68, NFPA 652 , NFPA 654, and NFPA 664, and, for additional information about combustible
dusts and combustible dust explosions.
For purposes of better determining the flammability for a 2 or 3 rating, the most important aspects are
particle size distribution, MIE, processing experience, housekeeping, and other related factors.
Additional information on combustible dust hazards can be found on the Occupational Safety and Health
Administration (OSHA) website at www.osha.gov. The following publications are recommended for further
reference:
Combustible dust explosions poster, available at https://www.osha.gov/Publications
/combustibledustposter.pdf.
Combustible dust explosions fact sheet, available at https://www.osha.gov/Publications
/combustibledustposter.pdf OshDoc/data_General_Facts/OSHAcombustibledust.html .
OSHA 3644, Combustible Dust: Firefighting Precautions at Facilities with Combustible Dust, 2013.
https://www.osha.gov/Publications OshDoc /OSHA_3644.pdf data_General_Facts
/OSHAcombustibledust.html .
OSHA 3674, Combustible Dust: Precautions for Firefighters to Prevent Dust Explosions QuickCard, 2013.
https://www.osha.gov/Publications/OSHA_3674.pdf.
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Committee Statement
Committee Statement: Added the new NFPA 652 to list.
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Second Revision No. 7-NFPA 704-2015 [ Section No. E.1 ]
E.1 Intrinsic Thermal Stability.
Thermal stability for hazard evaluation purposes can be done by a number of methods. Frequently used
techniques include differential scanning calorimetry (DSC) and accelerating rate calorimetry (ARC). These
tests should be performed in a manner meeting or exceeding the requirements outlined in ASTM E537,
Standard Test Method for Assessing the Thermal Stability of Chemicals by Methods of Differential
Thermal Analysis, or ASTM E1981, Guide for Assessing the Thermal Stability of Materials by Methods of
Accelerating Rate Calorimetry.
Obtaining the instability rating through testing and I i nstantaneous P p ower D d ensity (IPD) data is
preferred. This method is discussed in Section E.2, and IPD takes precedence over other small-scale
calorimetric methods. When data are unavailable to apply the IPD method, the following two alternatives
are available: D d ata from DSC or ARC (or their equivalent) can be used to determine the calculated
adiabatic exotherm initiation temperature. This can be used to define ratings of 0, 1, or 2.
Materials that exhibit calculated adiabatic exotherm initiation temperatures below 200°C (392°F) should
be rated at least 2; materials that polymerize vigorously with evolution of heat should also be rated at least
2.
Materials that exhibit calculated adiabatic exotherm initiation temperatures between 200°C (392°F) and
500°C (932°F) should be rated 1; materials that might polymerize when heated should also be rated 1.
Materials that do not exhibit an exotherm at temperatures less than or equal to 500°C (932°F) should be
rated zero.
Professional judgment should be applied to a chemical being rated using this method that might have an
instability rating of 2 or greater.
Reactive materials are far more likely to suffer catalytic or surface effects in small test containers, hence
biasing the calculated adiabatic exotherm initiation temperature.
This judgment should include comparisons with the qualitative criteria described in Table 7.2 , analogy with
chemicals of similar chemical structure and historical incidents, plus data obtained using the following
methods.
Information to assist this professional judgment includes, but is not limited to, data obtained via DSC or
ARC. ASTM D2879, Standard Test Method for Vapor Pressure–Temperature Relationship and Initial
Decomposition Temperature of Liquids by Isoteniscope, can be used as an indication of thermal stability
when data meeting the requirements of ASTM E537 are not available. Self-A a ccelerating
D d ecomposition T t emperature (SADT) test results can also be used. Alternatively, calculations based
on the ASTM computer program CHETAH® could be carried out. (For further information on CHETAH,
see E.3 .)
It should be noted that tests performed in small-volume analytical apparatus are not predictive of the
explosive behavior of large masses of material and therefore cannot distinguish instability ratings of 3 and
4.
Appropriate testing should be conducted for mixtures because the mixtures might react differently than
indicated by the individual components.
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The exotherm initiation temperature is a function of the sensitivity of the instrument and the choice
of the instrument. The measured exotherm initiation temperature can be corrected to give a
calculated value that approximates the ideal “adiabatic value”. By adding the word “calculated” in
front of “adiabatic” the variability of test instruments and analytical techniques is allowed for. See SR
2 related changes made to Table 7.2.
A reference to new E.3 added in SR 8 has been noted.
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Second Revision No. 8-NFPA 704-2015 [ New Section after E.2 ]
E.3 CHETAH.
CHETAH is a computer program that is useful for several tasks, including the following:
(1) Characterizing materials for their ability to decompose with violence
(2) Estimating heats of reaction or combustion
(3) Predicting lower flammability limits and certain other flammability parameters
(4) Predicting thermochemical properties such as standard enthalpies of formation, heat capacities,
and free energies of formation
An extensive database of common chemicals, primarily organics, is included in the program, along with
a procedure to predict values for additional chemicals using the Benson group additivity method of
describing molecules from molecular fragments.
For hazard evaluation, CHETAH is a conservative screening tool for use during the early stages of
compound synthesis or process development. Its use should be integrated within an experimental
program for testing reactive chemical hazards. CHETAH was not designed to replace the physical
testing of materials. Rather, CHETAH’s computational results should be used to complement
experimental results to help identify the need for further testing in the areas of impact sensitivity and/or
flammability.
The potential hazards associated with handling new chemicals will not, in general, be known a priori.
Furthermore, experimentally determined thermochemical data for new chemicals used for process
design and to predict hazards will often not be available. CHETAH exists largely to allow users to build
compounds using group additivity methods, to predict thermochemical properties for compounds and
reactions, and to use these predicted properties for hazard evaluation. Users can then use CHETAH’s
predictions with results from accelerating rate calorimetry (ARC), differential scanning calorimetry
(DSC), drop-weight, or other tests to prepare, use, store, or dispose of new compounds safely.
Personnel committed to ensuring the safe operations at sites where research, process development, or
manufacturing occur could find CHETAH useful in reactive chemicals evaluation programs.
The user might wish to examine the following list of references for examples illustrating how CHETAH
can be used to evaluate instability hazards. A more extensive list of references concerning CHETAH
can be found at:
www.astm.org/BOOKSTORE/PUBS/DS51F.htm. CHETAH is distributed by ASTM International Inc.
References:
Britton, L. G.; Frurip, D. J. “Further Uses of the Heat of Oxidation in Chemical Hazard Assessment,
Process Safety Progress,” 22 (1), 1–19, 2003.
Frurip, D., et al., “The Role of ASTM E27 Methods in Hazard Assessment: Part I. Thermal Stability,
Compatibility, and Energy Release Estimation Methods, Process Safety Progress,” 23(4), 266–278,
2004.
Pasturenzi, C., et al., “Thermochemical stability: A comparison between experimental and predicted
data, Journal of Loss Prevention in the Process Industries,” 28, 79–91, 2014.
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Committee Statement
Committee
Statement:
Annex E.3 has been added to better describe CHETAH. This addition is offered in view of the fact
that NFPA Appendix E makes mention that CHETAH may be useful in the evaluation of instability
hazards but makes no mention of CHETAH otherwise. The user of NFPA 704 might benefit from a
short description of CHETAH and indicates the source for this tool.
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Second Revision No. 9-NFPA 704-2015 [ Chapter G ]
Annex G Comparison of NFPA 704 Numerical Hazard Rating with OSHA’s /UN Numerical Hazard
Classification System.
This annex is not a part of the requirements of this NFPA document but is included for informational
purposes only.
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G.1
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NFPA and the Technical Committee on Classification are aware of the potential impact that the G g lobally
H h armonized S s ystem (GHS) incorporation into OSHA’s Hazard Communication Standard (HazCom)
2012 has on the NFPA 704 standard system and its users. Currently, NFPA 704 stands as written and
there is no immediate plan to change the system. NFPA 704 is widely used and recognized by emergency
responders and safety personnel for identifying the hazards of short-term/acute exposure to materials
under conditions of fire, spill, or similar emergencies. The Committee will carefully consider any impact
before changing a consensus standard system that has been protecting emergency responders,
employees, and the public for over more than 50 years.
The NFPA 704 diamond remains as a ’ stop warning sign‘ for first responders. It provides information
required for the first responders to assess hazards presented by materials within an occupancy or
industrial location. It provides, in a concise format, a quick presentation of all hazardous materials present.
This provides critical size-up information needed to evaluate potential short-term exposure to the
hazardous materials within the facility against first responder training and personal protective equipment.
From this initial information, informed decisions can be made about the next steps to take to protect
responders and the community and what additional resources might be needed to mitigate the event.
OSHA and NFPA are in agreement that there are differences between HazCom 2012 and NFPA
704, ; because the two systems were developed for different purposes. There are two distinct sets of
numbers used for the two systems: HazCom 2012 uses a hazard classification system whereas NFPA 704
uses a hazard rating system. The NFPA 704 label was developed to provide information to emergency
personnel responding to a spill or fire. In comparison, OSHA’s H h azard C c lassification S s ystem
provides information for workers exposed to materials primarily under normal conditions of use. The
numbers that are part of the OSHA HazCom 2012 hazard classification system are then used to obtain
more detailed information for labels and safety data sheets in Appendixes A, B, and – C of the OSHA
standard. In contrast, the numbers in NFPA 704 are relative ratings of hazards developed for emergency
response.
HazCom 2012 numbers are included in Section 2 of the new S s afety D d ata S s heet (SDS) format. The
concern is that these numbers could be mistakenly identified as NFPA 704 ratings and be transcribed to
the NFPA 704 label diamond . Because the two systems have inverse number systems (e.g., 4 is the most
hazardous rating in NFPA 704 but the least hazardous in OSHA’s GHS classification), a transcription error
could lead to incorrect identification of the hazard in an emergency response. It should be noted that the
hazard classification numbers are not required on HazCom 2012 labels.
Both systems have value for different purposes. The key to distinguishing the two systems is education.
NFPA and OSHA developed a ‘Quick Card’ to explain the two systems and their differences. (See Figure
G.1.) This card is also available for download at www.nfpa.org/704 under ‘ Additional Information’ on the
first tab, and on the OSHA website at: www.osha.gov/Publications/OSHA3678.pdf . You can also sign up
for email alerts at the top of the document information page at www.nfpa.org/704 to receive an email alert
when any additional NFPA 704 document-related information is posted to the page. NFPA will continue
discussions with OSHA and with emergency responders to insure ensure that all concerns are addressed.
Figure G.1 ‘ Quick Card, Front and Reverse Sides ’ .
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Committee Statement
Committee
Statement:
Editorial changes were made for clarity. References to GHS were removed since the
comparison is to the OSHA HazCom standard that incorporates GHS but not to GHS itself.
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Second Revision No. 3-NFPA 704-2015 [ Section No. H.1 ]
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H.1
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NFPA frequently receives requests for permission to use the NFPA 704 diamond in safety and emergency
response publications and training materials. This annex is provided as an example of labels and text that
can be used within publications and training documents that summarizes the NFPA 704 label system.
[See Figure H.1(a) and Figure H.1(b).]
Figure H.1(a) NFPA Sample Placard 1.
Figure H.1(b) Hazardous Materials Classification.
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The following text should accompany the placard examples published in any document:
NFPA 704 provides a simple, readily recognizable, and easily understood system of markings that
provides a general idea of the hazards of a material and the severity of these hazards as they relate to
emergency response. The standard does not tell you when such labels are required but provides the
criteria for labeling when such labels are required by another code, standard, regulation, or jurisdiction.
The ratings shown in Figure H.1(a) and Figure H.1(b) are in summary form only. The current edition of
NFPA 704 should be consulted for the detailed criteria used to determine the correct numbers to be
placed in the quadrants for a specific material.
Reprinted with permission from NFPA 704-2017, System for the Identification of the Hazards of Materials
for Emergency Response, Copyright © 2016, National Fire Protection Association. This reprinted material
is not the complete and official position of the NFPA on the referenced subject, which is represented solely
by the standard in its entirety. The classification of any particular material within this system is the sole
responsibility of the user and not the NFPA. NFPA bears no responsibility for any determinations of any
values for any particular material classified or represented using this system.
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Committee Statement
Committee
Statement:
The Committee agreed to change the title as suggested and to rotate Figure H.1 (b) to be
consistent with the NFPA 704 symbol in use. However, the Committee is retaining the health rating
description as written to be consistent with the degree of hazard descriptions used for hazard
degrees 1-4 as taken from Table 5.2. The "essentially non irritating" language taken from Annex B
refers only to skin, eye contact.
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Public Comment No. 4-NFPA 704-2015 [Section No. H.1]
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Second Revision No. 5-NFPA 704-2015 [ Section No. I.1.1 ]
I.1.1 NFPA Publications.
National Fire Protection Association, 1 Batterymarch Park, Quincy, MA 02169-7471.
NFPA 30, Flammable and Combustible Liquids Code, 2015 edition .
NFPA 68, Standard on Explosion Protection by Deflagration Venting, 2013 edition .
NFPA 400, Hazardous Materials Code, 2016 edition .
NFPA 652, Standard on the Fundamentals of Combustible Dust , 2016 edition.
NFPA 654, Standard for the Prevention of Fire and Dust Explosions from the Manufacturing, Processing,
and Handling of Combustible Particulate Solids, 2017 edition .
NFPA 664, Standard for the Prevention of Fires and Explosions in Wood Processing and Woodworking
Facilities, 2017 edition.
Fire Protection Guide to Hazardous Materials, 14th edition, 2010.
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Committee Statement
Committee Statement: Reference added.
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Second Revision No. 10-NFPA 704-2015 [ Section No. I.1.2.3 ]
I.1.2.3 Other Publications.
American Coatings Association, Hazardous Materials Identification System Revised, Implementation
Manual, 1981.
Bretherick, L., Handbook of Reactive Chemicals, 7th edition, Boston: Butterworths, 2006.
Britton, L. G., “Survey of Fire Hazard Classification Systems for Liquids,” Process Safety Progress, Vol.
18, No. 4, Winter, 1999.
Britton, L. G., Frurip, D. J. “Further Uses of the Heat of Oxidation in Chemical Hazard Assessment,
Process Safety Progress,” 22(1), 1–19, 2003.
Frurip, D., et al., “The Role of ASTM E27 Methods in Hazard Assessment: Part I. Thermal Stability,
Compatibility, and Energy Release Estimation Methods, Process Safety Progress,” 23(4), 266–278, 2004.
Hanley, B., “A Model for the Calculation and the Verification of Closed Cup Flash Points for
Multicomponent Mixtures,” Process Safety Progress, Summer 1998, pp. 86–97.
Hofelich, T. C., “A Quantitative Approach to Determination of NFPA Reactivity Hazard Rating Parameters,”
Process Safety Progress, Vol. 16, No. 3, p. 121, 1997.
Hofelich, T. C., D. J. Frurip, and J. B. Powers, “The Determination of Compatibility via Thermal Analysis
and Mathematical Modeling,” Process Safety Progress, Vol. 13, No 4. pp. 227–233, 1994.
Hofelich, T. C. and LaBarge, M. S., “On the Use and Misuse of Detected Onset Temperature of
Calorimetric Experiments for Hazardous Chemicals,” Journal of Loss Prevention in the Process
Industries , Vol. 15, pp. 163–8, 2002.
Laidler, K. L., Chemical Kinetics, Chapter 3, New York: McGraw-Hill, 1965.
Pasturenzi, C., et al., “Thermochemical stability: A comparison between experimental and predicted
data,” Journal of Loss Prevention in the Process Industries, 28, 79–91, 2014.
Stull, D. R., “Fundamentals of Fire and Explosion,” AIChE Monograph Series, No. 10, Vol. 73, 1977.
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Committee Statement
Committee Statement: Added reference for information used to revise Annex E.
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